Method of curing cement-type cold molding compositions



1 n @RUSS Inventor: Rov'lad W. Staey, by MC2...

His, Attorney.

Patented Feb. 7, 1950 METHOD OF CURIN-G CEMENT-TYPE CGLDJ MDLDING COMPUSITIONS Ronald W. Staley,E Pittsfield. Mass.x asslgnor il! General Electric Company... a corporation. of.

New Yorkv Application November. 8, 19%, Seal- G-'Claimm (Cl. I8--4'll lA This invention is concerned with new' cementftions (refractory) compositions of' matter and" methods of making'the same. More particularly, this invention relates to a. method oi' curing' a; shaped article comprising a mixture' of ingredients containing a Portland cement. and a suhstantlally non-acidic filler, which method' compri-ses concurrentlysubjecting the said article; under pressure, to an atmosphere comprising. from approximatelyo to 20 mol per cent'fcarbon' dioxide (in the gaseous state)` and conversely from approximately 20 to 80 mol per cent sub'- stantially dry steam.4

In the iield of' cold-molded compositions ot" matter comprising substantially inorganic materials,'. shaped articles prepared from a mixture of materials comprising ground' Portland cement binder and an inorganic 1111er (usually inthe form' of'ilbers' or' also iinely zround have' assumed a position.. of great importance. Such 20 types' of materials are especially suited for the. manufacture of are' chutes. circuit breakers, and.' for' other articles of`manufacture. where non'- inilammability is' of the. utmost importance. In:

addition, cold-molded articles', because ofthe ea'se with which they can be adapted to mass' production techniques. are employed' for such' articles of manufacture" as' knobs. switch bases: terminal insulators, control panels, etc.

Present day techniques for making' cold molded products comprise mixing the cementitious bind-'- er` with an inorganic illler; molding the artieie.4 to shape for a veryshort'time, e. g.-. for abouti5 seconds, in a cold mold' or in a'moid which has been heated somewhat, and thereafter' removing 35 the molded article tromV themoldand subjecting it to an atmosphere. which sets the cement or.. as it is often called'r cures. the. cement. Various. methods have been employed. toenact the curing'.

oi'. the cement'v Several of theseemethcds com- 40 prise treating. the cold-molded: article with, e. 32.-. steam, or carbon or first with a water' tog? and thereafter immersion the articles ini water for'. varying lengths or time.` By meanrat` these' treatments the cementV is'. curedto an an preciable extent and fair strengthsresult. How everr such. treatments leave much to be desired'. For instance, when the steam treatmentA alone k. employed to: cure the-shaped' article, it is believed...

by manyA authorities that thePortland' cement. 50

isA changed from. the tricalciunr silicate form to'- the dicalcium silicate form in accordance with the following equation:

In this case, when no acidic material isx present' I a. substantial amount of. an acidic ller. e. 3.a o0

silica.. to react with the lime However, the use .Ndumrhasthg disadvantage v that it occupies space ordinarily taken up by'ilbrous. which` reinforce the article. This results in' a loss strength` nearly' compensating for the gain ob.- tained in. using the silica'. Thus, the advantage' obtained'. by using substantially non-acidic llllers; e. g., asbestos iloats',y short or long asbestos bers. etc'., which ordinarily add greatlyito the strength of the cold-molded article, is nulliiied.v

When carbon dioxide (gaseous carbondioxldell alone is employed to treat the cold-molded- Portl'and'- cement product, the CNDH): present in the cement reactswith the carbon dioxide to form insoluble. CaCO's- However, it is diiil'cult to ob# tain sulcient saturation of the Portland' cement. with the carbon dioxide to convert all the CaCOH'Ia to the more. desirable insoluble CaCO'a.- Ifwater la depended. upon to formaqueous carhonfc acid with; thecarbon dioxide, the aqueous carbonio acidlnthe. presence oi an excess oi. carbonio acid. gas forms with hydrated lime., acidic calcium bicarbonate., the acidic'bicarhonate decomposinginto an4 in soluble carbonate. However.. this process pred fcates its success on.y an abundance of moisture, l

and in view of the fact that carbon'dioxlde has s limited solubility in, even cold' waterw and. decreases as the temperature increases', the. conversion of the lime under suchV conditions is incomplete. This diillcutly-is also, presentin the usual process of curing cement compositionsof mattei:` with high pressure wet steam and. carbon dioxide;i that is,.- the carbonation is confined tothe outer surface oi the object being treated and does not penetrate' into the interior,A thus resulting in an interior product oi poor strength.

I" have now discovered. that shaped compositionsofmatter comprising Portland cement as a binder and; containing a substantially non-acidic lllIer Ican be treated concurrently with both carbon dioxide and substantially dry steam to yield articles having strengths heretofore unobtainablel by the methods now known. to the art. ItV was surprising to discover that the concurrent. steam and carbon dioxide cycle could accomplish this because of the aforementioned limited solubility of carbon dioxide in even moderatelywarm water.

In the practice of my invention, the' concurrent use of the dry steam and carbon dioxide (gaseous carbon dioxide) can be utilized to itsfullest-extent only if certain conditions are rigidly en forced. One of the conditions consists intellect-r ing contact betweenthe shaped article and thev treating medium while the whole system is under pressure. Inaddition, the steam employed should be. substantially dry steam. This. of. course, necessitates treating the shaped'. articles at temperatures. ot'at least above about 100 C.. Furthermore, to. obtain the. desired. results, itis essential that the carbon dioxide and dry steam.. be. present within. certain proportions, namely,.. from approximately 8o to 2o mol' per: cent carbon tlowable mixture,

3 dioxide and conversely from approximately 20 to 80 mol per cent substantially dry steam. Optimum results are usually obtained when the two gases are employed within limits ranging from approximately 60 to 40 mol per cent carbon dioxide and conversely from approximately 40 to 60 mol per cent substantially dry steam.

percent of the -weight of the dry-ingredients (Portland cement and ller) may also be incorporated to increase the ow of materials in the mold. The compound is formed in steel molds To derive the optimum benets from my invention, it is essential that a substantially nonacidic filler, or to 10 per cent of the weight of the total ingredients. Examples of acidic llers However,'srna1l amounts of cold or heated) under pressure removed from the molds vand thi'TfEEf-eably allowed to set in air for varying lengths of time, e. g., from -about 2 to 10 hours, or until the initial set has taken place. It is, of course, understood that though the step of allowing the shaped article to set in the air is highly desirable and important,

- the length of time during which the air-set takes which may be used with the non-acidic llers in these proportions are silica (SiOz), 1 al2e.

diatomaceous earth etc. It is -not exactly understood why outstanding results are obtained using a substantially non-acidic iller. However, it is believed that the use of an acidic filler results in the acidic ller competing with thev carbon dioxide for the Ca,(OH)a freed in the process,

Awith the result that there is less CO2 taken up and therefore less CaCO: formed to ll the voids and reinforce the structure. In such a case, after the cure treatment, much less CO2 has been found to be incorporated into the structure than if the filler consisted substantially of non-acidic material.

The proportion of Portland cement` to the substantially non-acidic filler may be varied over a wide range. Good results are obtained when, by weight, the Portland cement comprises from about 25 to 95 per cent, preferably from 35 to 65 per cent, of the mixture comprising Portland cement and the substantially non-acidic ller. Substantially non-acidic llers which may be employed""wt e Portland cemen a asbestos, for instance asbestos floats, short asbestos bers, long asbestos iibers, etc., granular llers, e. Nmica, olivine, doloite, magnesite, `fellspar,(talc,) etc. 'I he amount, by weight, of the non-acidic fllerrpresent may range from about 5 to '75 per cent, preferably from 35 to 65 per cent, of the total weight of the non-acidic iiller and the Portland cement, the total percent of the ingredients, including the ller and Portland cement, being equal to substantially 100 per cent. Small amounts of calcium hydroxide may Abe used advantageously to increase the amount of CO3 reacted with the mass and to further increase the strength properties. A useful range Vof ingredients whichimay be employed comprises the following materials in the designated per cents by weight:

A Per cent Portland cement 35 to 95 Substantially non-acidic ller e. g., as-

`bestos 6,5to 5 Acidic flller 0 to 10 Lime (calcium hydroxide) 0 to 5 Plasticizer, e. g., kaolin clay 0 to l0 The percentage of each component is so chosen that the total'is equal to 100 per cent.

Various procedures may be employed to carry out the practice of my invention. One of these comprises molstening the mixture of Portland cement and i-lller with a suilicient amount of (for example, to 25 per cent Water based lplace is not critical. For instance, tests have shown that shaped articles which have been allowed to set in the air for a period of time as long as six months were advantageously treated in accordance with the embodiments of my invention; this indicates that my claimed process of treat- ,ment is not dependent upon an optimum water content in the shaped article before the treat ment with carbon dioxide and steam. l After the shaped part has set for a sulcient i length of time, it may then be placed in an autoclave where it is treated with the carbon dioxide and dry steam mixture. Any apparatus suitable for the purpose may be used in which the shaped article may be subjected to the mixture of gases (carbon dioxide and dry steam). The figure in the accompanying drawing is a diagrammatic view of a suitable apparatus for carrying out the claimed process.

The apparatus shown in the drawing comprises v essentially an autoclave, the general structure of on the weight of the solid materials) to form a which is well known in the art. Carbon dioxide is supplied from a high pressure container through a. pressure reducing valve and enters the jacket 3 through the inlet pipe 2. Heating or the autoclave is accomplished e. g., by means of steam which is supplied to the steam jacket at high pressure through a pressure reducing valve and lenters the jacket through the inlet pipe 4. The steam return pipe is shown at 5. The shaped (molded) article (or articles) 6 to be cured is placed in a basket l which is supported on a tripod 8. The water supply or source 9 for generating steam. i. e.. the dry steam which is to be mixed with the incoming carbon dioxide, is located in the bottom of the autoclave I and may be drawn oft' through water outlet pipe l0.

'I'he heating steam should be supplied through the steam Jacket at a high enough pressure to produce the required steam pressure on the outside of the autoclave. I have found, for example, that if 40 pounds per square inch autoclave (internal treating atmosphere) steam pressure is desired, about pounds per square inch Jacket pressure is usually required. In the operation of the apparatus the steam is introduced into the outer Jacket throughout the curing cycle. Excess 4water is at al1 times available in the form of a p ool at the bottom of the autoclave. However, it is `to be understood that despite the presence of the pool, the steam is substantially dry since the temperature of the treating atmosphere is at least C. v

It has been found that if temperatures of from about 100 to 150 C. or higher are used, this willpreclude the possibility of any water droplets being present above the pool of water in the autoclave treating chamber (for brevity herein after referred to as the autoclave) This is important for the reason that, since the water and carbon dioxide are in the form of gases, they are in a dynamic state of activity, and capable of greater penetration than if in the form of liq- Ik'crosseessuiei materialsi. ez. 5,. styrene,etc;,. drying. oils-. cumar pressure of 80 pounds per square inch. Thus` if the steam pressure inside the.l autoclave is 40T, pounds per square inch; then'- the-partial pressurel` of the carbon dioxide will be about pounds pen` square inch,.because the difference between the total autoclave. pressure and the: internal pressure of' the steam maybe assumed to be thepar'- tialpressurefoi the-carbondioxide. For. my purposes-.1, obtain.good results. when the total. auto-- clave. pressure (internal) ranges fromabout. to 1'75 pounds per square inch. It'. Will-be: understood. by those=skilled inthe art.. that the. length of time during. which. the shaped article isgsubiectedto. the mixture 4of carbon. dioxide and: substantially dry steam. may be varieddepending on several factors, includingre. g.,.th`e; size ofthe'- shaped article, the number of'articles being treated, the pressures employed, etc. Usually the time employed for treating the article will advantageously range from about 6 to as long as 24 or 48 hours. Generally, for each one-quarter inch thickness, the dry steam-carbon dioxide treatment should' be carried' out for from about 3 to 6 hours.

After treating the shaped article, it is removed and usually, bakedat. elevated temperatures,- e. gm 1511"' to. 2ll0` C2, tofremove. any residual. moistureWliiohlmayY have condensed onthe. parts in` cooling the autoclave prior to opening it and'removing the parts. Although after-baking is not absolutely essential, whereincrease in strength is the only requirement, it doesimprove the electrical properties of thearticles.E The electrical properties of the shaped article may be" further improved by impregnating the cured" article with'. various impregnants for that purposee. g., sub-` stantially. water-insoluble impregnants, for instiazn'o'e,` paraiiin' wax, cashew nut shell' liquids (especiallythose comprisinga phenol.' having onf` its" nucleus` a; 14 to. 28 carbonatom unsaturatedV Hydrocarbon" substituent whose unsaturation. is.. desolely to one or more ethylenic linkages andl particularly with' that' group of saidY plienols.Y

which' includes those liquids derived.' from the` Anacardlaceae' family o f' plants and'certainconstituents and derivatlvesthereofi which compositions are a fraction ofcashew nutshell liquid sold, e. g., by the-Irvington Varnish and. Insulatorv Companyof Irvington, New/Jersey), heat convertible synthetic resins, heat polymerizable resirn(paracoumaronetindeneresinsssold: erg., by! theBarretirDivision ofthe Alliedzchemicaklom pany), etc.

In order that those skilled in the art-maybetter understand. how the: present invention may be practiced. the following; examples' aref; given .by way of illustration and' not by way of limitation. All parts. are by weight.

In the following examples, the method of mix-f ing the ingredients comprised moistenlng them-- gredien'ts with about 15' percent water based on' tiie weight: of the dry' materials and? thereafter mixing:them:thoroughlyr in a'double-armeddbught mixer (Baker-Perkinm mixer). compound thus. obtained was molded to shape'in:

aisteel' compression mold for about 5 seconds at'' Ingredient Prts Portland cement 550 Asbestos floats l(short tibers); 240" Mediumlon ,Canadian chrysotile asbestos fibers actslin'clay used for plasticizing purposes) 1% a Pl' The `above molding composition wast' molded' into` the form ofv bars- (0.5." X015 x 5") and disks.'- (4. in diameter by 0l25!"`thick).. The bars and? disks were' treated' in; the previouslydescribed autoclave at thefpressures specified below. Un'y less stated otherwise,. the length of treatment.

was for about 8 hours and the air set, i.,e., the g length of' timeduring' whiclr the molded pieces were allowed to set in theair after the molding operation prior to the treatment in the auto.- clave, was approximately 15' hours. As a control, some of. the' disks and bars were subjected to the usual commercial treatment given coldmolded articles' of this type. This consisted in subjecting the air-set pieces to a moist (fog)' atmosphere for 24 hours and then immersing the, pieces in water. for another 24 hours; this' was followedby a bake for about 20 hours at approximat'ely 1755?'0':

I'InSam less and 9', cured and baked specimens of Sample l were subjected to as carbondo de pressure of 50 s.l iffor 24 hours in the autoclave (in the case of Sample 8) and to a carbon. dioxid hours inthe autoclave (in the case of Sample 9).

ry steam treatment at p. s: i. total pressure for 2 42 ll the treated specimens were baked.-

at 150 C'. for l5 hoursand' then tested'w-ith the above results.

i In. Sample 1D, the carbondloxidefsteam treatment was continued: for-24 hours 'er thefdesignated. fessure instead fof the 8 hours used for Samples 2-7.

r Pere en: weight inereasovertheweightmi sampled.-

2,4oc,sos

Water Abso tion 24 ours Dielectric Insulation 38111910 N 0. Mtan Per Cent Volts/Mil 16 0.

Three disks of each set obtained lfrom Samples 1 and 7 were immersed in a high melting point paraffin wax, cumar CX resin (manufactured by Barrett Division of Allied Chemical and Dye Corp.) and Cardanol No. 923 (manufactured by Irvington Varnish and Insulator Co.,v obtained from cashew nut shell liquid and comprising essentially the phenol having the formula CzoHazO. and commonly known as Cardanol) at 130 C. for about hours. The disks were rinsed in xylene to remove the excess impregnant from the surface. The disks impregnated with Cardanol 923 were baked at 150 C. for 15 hours. All the disks were tested for insulation resistance before and after 24 hours immersion in water, 4 hours later, 24 hours later, and 48 hours later. The method of testing was according to test method No. D257-38 as specied by the American Society for Testing Materials. Following are the results of the various tests:

Description of disks Per Cent By Sample No. Type Cure Impregmnt Veiaght n?.

bsorbed Parailln Fog and water-. .do

Insulation resistance in megohms 24 Hours Later After 24 Hours in Water 4 Hours Later 48 Hours Later The above electrical insulation resistance results demonstrate conclusively the. advantage obtained by impregnating cementitious cold-molded articles which have been previously treated in accordance with the embodiments of my invention.

' Moreparticula'rly, the treatment with the carbon dioxide-dry steam mixture improves considerably the ability of the impregnated article to recover -its electrical resistance after water immersion.

impregnating agents or impregnants in additionto the ones employed in the foregoing example, may be used to advantage to improve the electrical properties of the cold-molded parts treated with my claimed dry steam-carbon dioxide process.

8 EXAMPLE 2 A molding composition was prepared in the same manner as in Example 1. This composition had the following formulation:

Ingredient Parts Portland-Puzzolan Cement l Asbestos iioats (short iibers) Medium long Canadian chrysotile asbestos ber: Kaolin clay 1 atar...

Flexllral,

Type Cure Lbs'lm.,

Fog and water--...

420 C02-Dry steam EXAMPLES Molding compositions were prepared in the manner shown in Example l. The formulations `of these molding compositions were as follows:

Ingredient Sample 13 Sample 14 Sample 15 Paru Park

Portland Cement ilx (silica or 810:)

A Water Bars were molded from the above molding compositions and specimen bars were cured using fog and water as in Sample 1 of Example 1, and using a carbon dioxide-dry steam treating medium. ('75 p. s. i. dry steam and 75 p. s. i. carbon dioxide) as employed for Sample '7 in Example 1. The bars were after-baked for 20 hours at 150 C., and tested for their strength characteristics with the following results:

Per Cent Weight Increase Over Fog- Water Cure Chmy Flexural vom ses: Lbs-fw Fog and water C03-Dry Steam-. Fog and Water. CO2-Dry Steam...

P99999 Bunn-INH ouen-x The results of tests conducted on the samples in '."this example demonstrate the effect of using an acidic ller such as silica. Under the conditions of treatment, the sand or silica functions as an -acidic material and competes with the carbon corresponding reduction in the carbon dioxide take-up results. This is reected in the large increase in weight of the sample containing talc dicte mfg.. 1...

accuses 99 (substantially non-acidic 1111er) as' the Allel: as compared to the sample containing the silex (silica) as the filler.

Ingredient Sample i6 Sample 17 Sample 18 Sample 19 Parts Parte Paris Parts Portland cement 550 550 650 540 Aslastfgs iloats (short 240 240 240 230 ers Medium .long Canadian 120 120 120 110 cbrysotile asbestos bers. Kaolin clay 80 80 30 Slaked lime 50 100 Water 150 150 150 150 The above mixtures were each molded into the form of bars as was done in Example 1. All the bars (with the exception of the bars prepared C02-Dry Ch Sample Steam amy Flexural, No. TYP@ Cure Raro, {.lglpfgg Lbs/m.:

Lbs./in.I

16 Fog and water 0. 27 4, 280

(control) 17 C02-Steam 75-75 0.33 710 18 do 75-75 0. 34 7, 290 19 do 75-75 0. 30 5, 531

From the foregoing results, it will be apparent that by means o1' my process of treating a shaped article comprising Portland cement and a nonacidic filler, I am able to obtain articles which possess strength substantially greater than those obtainable by the usual methods heretofore em-vployed in the art. Such results are obtainable only if a substantially non-acidic iiller is employed and the treating conditions are confined to a medium consisting of dry steam and carbon dioxide, the latter two gases being present within specific ranges, namely, from approximately 80 to 20 mol per cent substantially dry steam. Optimum results are obtained when the carbon dioxide and the substantially dry steam are present in about equal mol per cents, e. g., the partial pressure of each gas is the same and wherein the total pressure of the two gases is from about 80 to 150 pounds per square inch.

I believe the products obtained by my process are substantially different from the products obtained by any method heretofore employed.

'14) This fact is evidenced by' the improvementsin properties which I am able to effect by the prac tice of my invention. This diierence is believed to beV due to the substantial lack of residual or free calcium hydroxide molecules in the ilnally treated product. By means of my claimed proc` ess, I am able to effect conversion of substan'- tially all calcium hydroxide molecules to the more desirable calcium carbonate form. .This conversion is reected in the increase of speciific gravity of the cold-molded product which increases, e. g., from about 2.00 to 2.25. This increase in specic gravity is not accompanied .by any measurable increase in size of the article,

indicating that my claimed process of treating ,cold-molded articlesv actually results in a decrease of the size of the voids present by the filling in of the said voids with calcium carbonate.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. The method which comprises (1) shaping a mixture of ingredients comprising a Portland cement and a substantially non-acidic filler, and (2) concurrently subjecting the shaped article, under pressure at a temperature of at least 100 C., to an atmosphere comprising from approximately 80 to 20 mol per cent carbon dioxide and conversely from approximately 20 to 80 mol per cent substantially dry steam 2. The method which comprises (1) forming into a definite shape a mixture of ingredients comprising Portland cement and a substantially non-acidic filler, (2) allowing the formed article to partially set, and (3) concurrently subjecting the said article under pressure at a temperature of at least 100 C. to an atmosphere comprising from approximately 80 to 20 mol per cent carbon dioxide and conversely from approximately 20 to 80 mol per cent substantially dry steam.

3. The method of curing a shaped article comprising a mixture of ingredients containing Portland cement and asbestos, which method comprises concurrently subjecting the said article, under pressure at a temperature of at least 100 C., to an atmosphere comprising from approximately 60 to 40 per cent carbon dioxide and conversely from approximately 40 to 60 mol per cent substantially dry steam.

4. The method of curing a shaped article comprising a mixture of ingredients containing Portland cement, asbestos, and a plasticizer for the said mixture, which method comprises concurrently subjecting the said article, under presi sure and at a temperature of from.100 to 150 C., to an atmosphere comprising from approximately to 4-0 mol per cent carbon dioxide and conversely from approximately 40 to 60 mol per cent substantially dry steam.

5. The method of'curing a shaped article comprising a mixture of ingredients containing, by weight, from 35 to 65 parts Portland cement and from to 35 parts asbestos, which method comprises concurrently subjecting the said article,

under pressure at a temperature of from to C., to an atmosphere comprising carbon dioxide and substantially dry steam, said atmosphere comprising from approximately 60 to 40 mol per cent carbon dioxide and conversely from approximately 40 to 60 mol per cent substantially dry steam.

6. The process of making a shaped article having good electrical insulation resistance and comprising a homogeneous mixture containing the following ingredients in the specified percentages by weight:

Per cent Portland cement 35 to 95 Substantially non-acidic 1111er 65 to 5 Acidic filler 0 to 10 Lime 0to 5 Kaolin clay 0 to 10 12 pregnating the shaped article with a cashew nut shell liquid comprising essentially Cardanol.

RONALD W. STALEY.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS 10 Number Name Date 130,952 Sprogle Aug. 27, 1872 461,888 Richardson Oct. 27, 1891 935,616 Todd Sept. 28, 1909 1,299,847 McCoy Apr. 8, 1919 1,431,962 Kempton Oct. 17, 1922 1,559,146

Andrews Oct. 27, 1925 

